Copolymers of acrylonitrile with nacroyl n&#39;-alanyl methylene diamides



Patented Feb. 3, 1953 COPOLYMERS F ACRYLONITRILE WITH N- A-CROYLN'-ALANYL METHYLENE DIAMIDES Ernst Zerner and Mark W. Pollock, New York,N. Y., assignors to Sun Chemical Corporation,

Long Island City, N. Y., a corporation of Delaware No Drawing.Application July 20, 1951, Serial No. 237,822

Claims. 1

The present invention relates to copolymers of acrylonitrile which areadapted to be formed into fibers, films and the like and which arefurther particularly retentive of conventional dyestuffs.

It is well known that polyacrylom'trile has properties which make thismaterial commercially valuable. For example, polyacrylonitrile may becast into self-supporting films or may be spun from solutions thereof toprovide fibers which are capable of being cold drawn, whereby thestructure of the fiber is molecularly oriented along the axis of thefiber to produce fibrous materials of high tensile strength. Thesematerials are further insensitive to water and to the common organicsolvents usually employed in dry cleaning operations. Therefore, suchfibrous materials have been found to be suitable for use in many of theapplications in which the common textile fibers are employed, and havefurther been found to provide more durable end products.

However, despite the seemingly apparent advantages of polyacrylonitrilefibers over those generally employed in the textile field, the use ofthe same in textile applications has been limited due to theinsensitivity of these materials to the conventional dyes employed tocolor fibers and fabrics of the ordinary textile materials such ascotton, rayon, etc. If, however, it were possible to providepolyacrylonitrile fibers, or fibers hav ing all of the desirable andadvantageous properties of polyacrylonitrile fibers, which fibers alsodisplayed an afiinity for conventional dyes and which were furtherretentive of such dyes, then it is believed that such fibers would inall probability find wide commercial use in the field of textiles andwould prove to be extremely valuable in many such applications.

The art discloses that various copolymers of acrylonitrile have beenprepared to meet this purpose. For example, U. S. P. No. 2,491,471discloses the preparation of copolymers of acrylonitrile withvinylpyridine which copolymers are said to be capable of furnishingoriented filaments of high tensile strength and also to be susceptibleof being dyed with acid dyes. In U. S. P. No. 2,531,408, there aredisclosed copolymerization products of acrylonitrile and itaconic acid,which products are said to be adapted to dyeing, particularly with basicdyes, and which are also adapted to the formation of molecularlyoriented shaped articles. In each of these cases, however, the copolymerobtained with the materials set forth therein is comparativelyexpensive. Therefore, one object of the present invention is to provideacrylonitrile copolymers which may be readily 2 cast intoself-supporting films or formed into molecularly oriented fibers,whichare adapted to be dyed with conventional dyes and which are highlyretentive of such dyes, and which furthermore are relatively inexpensiveto produce.

The above object is accomplished, according to the present invention, bycopolymerizing acrylonitrile with N-acroyl N-alanyl methylene diamides,corresponding to the general formula where R, is a member of the groupconsisting of hydrogen and methyl, and where Y is the residue of acompound selected from the group consisting of aliphatic amines,alicyclic amines and heterocyclic amines, which amines have at least onehydrogen attached to the amino nitrogen thereof, the point of attachmentof the said residue bein at the amino nitrogen thereof. The copolymersthus formed are particularly receptive of acid dyes.

Methylene diamides of the above type are described in a copendingapplication Serial No. 85,038, filed April 1, 1949, in the name ofPhilip P. Dalton, and now abandoned. As described therein, suchcompounds may be prepared by reacting a methylene-bis-acrylamidecorresponding to the formula R o H n 0 R CH2=-' I ICHrI I-'C IK J=CHswhere R represents hydrogen or a methyl radical, with a primary orsecondary aliphatic amine under such conditions that saturation of onlyone of the terminal unsaturated groups of the methylene-bis-acrylamideby the amine is effected. The compounds thus formed may be considered tobe amine mono-addition products of the methylenebis-acrylamides. Byselectively effecting the reaction between the amines and themethylenebis-acrylamides such that saturation of only one of theterminal unsaturated groups of the methylene-bis-acrylamides iseffected, the resulting addition products are capable of undergoingfurther reaction involving copolymerization of the addition productswith other polymerizable monomers.

In accordance with the present invention we have found that thosemethylene-bis-acrylamides in which only one of the terminal unsaturatedgroups thereof has been converted into a saturated grouping by reactionwith aliphatic, alicyclic or heterocyclic amines, which amines have atleast one hydrogen atom attached to the amino nitrogen atom thereof, maybe reacted with acrylonitrile to furnish copolymerization products whichmay readily be formed into molecularly oriented fibers and which arereadily receptive and retentive or" conventional acid dyes. lhecopolymerization products of the present invention contain principallyacrylonitrile, the ratio of acrylonitrile to the amine mono-additionprodnets of the methylene-bis-acrylamides employed, being generallywithin the range of approximately 90% to 99% by weight of acrylonitrileto approximately 1G% to 1% by Weight of the said amine mono-additionproducts.

Illustrative of various amines which may be utilized to provide theamine mono-addition products of the methylene-bis-acrylamides employedin preparing the copolymers of the present invention are methylamine,ethylamine, butylamine, decylamine, benzylamine, phenylethylamine,monoethanolamine, diethylamine, diethanolamine, cyclohexylamine,morpholine, piperionitrile are illustratively set forth in the followingexamples. All proportions are given in parts by weight.

Example 1.Formation [of the diethylamine mono-addition product ofmethyZene-bis-acrylamide In a suitable reaction vessel there are placed4.6 parts of methylene-bis-acrylamide dissolved in a mixture of 70 partswater and parts acetone. To this solution there is slowly added withstirring a solution of 2.2 parts of diethylamine in a mixture of 2 partsacetone and 8 parts water. The complete mixture is then heated at atemperature of 40 to C. for approximately hours to insure substantiallycomplete reaction between the reacting materials. The reaction mixtureis then allowed to stand for approximately 24 hours, after which time itis filtered to remove any insoluble material which may be present. Thefiltrate is then allowed to evaporate to dryness, there being obtainedapproximately 6.8 parts of a material consistin essentially of acompound corresponding to the formula In the above example, as in eachofthe illustrative examples describing the formation of the additionproducts of the methylene-bis-acrylamides, a 20% excess of the amineabove the theoretical molecular amount required to eifect the desiredreaction is employed to avoid the possible presence in the reactionproduct of unreacted methylene bis-acrylamide.

Example 2 One part of the product obtained in Example 1 was dissolved in19 parts of freshly distilled acrylonitrile and the solution was thenadded to a solution of 0.4 part of ammonium persulfate and of 01 part ofsodium bisulfite in 180 parts water. The pH of this solution was thenadjusted to apI-I value of 3 to 4 with dilute sulfuric acid. The"solution thus obtained was heated for approximately 3 hours at atemperature of 50-60 C. and was then allowed to cool and to stand atroom temperature with occasional agitation for two days. At the end ofthis time a white precipitate had formed which was separated byfiltration and air-dried. The material thus obtained was a copolymercontaining approximately by weight of acrylonitrile and approximately 5%by weight of the diethylamlne mono-addition product ofmethylene-bis-acrylamide.

A self-supporting film of the copolymer of Example 2, obtained bycasting the same from a solution of the copolymer in dimethyl formamide,was immersed for approximately one-half hour in a boiling aqueoussolution of Alizarine Sapphire SE, an acid dye manufactured by theNational Aniline Division of Allied Chemical and Dye Corporation. At theend of this time, the copolymer film was found to be dyed a deep bluecolor. A film of polyacrylonitrile, treated in the same manner, wascompletely unaffected by the dye.

Example 3 Formation of the butylamine mono-addition product ofmethylene-bis-'nethacrylamide.

Following the procedure set forth in Example 1 except that a reactionmixture is employed which consists of a solution of 18.2 parts ofmethlyene-bis-methacrylamide in a mixture of 280 parts of water andparts of acetone and to which solution a solution of 8.8 parts ofbutylamine in a mixture of 8 parts of acetone and 32 parts of water hasbeen added, there is secured a product which consists essentially of acompound corresponding to the formula A copolymer of. acrylonitrile andthe butylamine mono-addition product of methylene-bis methacrylamide wasprepared in accordance with the procedure set forth in Example 2utilizing 0.5 part of the product of Example 3 to 19.5 parts ofacrylonitrile. The copolymer thus obtained was one containingapproximately 2.5% by weight of the butylamine mono-addition product ofmethylene-bis-methacrylamide to 97.5% by weight of acrylonitrile.

A film, cast from a solution of such copolymer in dimethyl formamide andsubjected to treatment for approximately one-half hour in a boilingaqueous solution of the acid dye mentioned hereinbefore, acquired apermanent blue color.

Example 5.Fcrm=ation of the morpholine monoaddition product ofmethylene-bis-acrylamide To a solution of 15.4 parts ofmethylene-bisacrylamide dissolved in a mixture of 280 parts of water and160 parts of acetone there are added 10.5 parts of morpholine dissolvedin 40 parts of a 20% acetone in water solution. The reaction is thencarried out in accordance with the procedure set forth in Example 1, theproduct thus secured consisting essentially of a material corre- Example6 weight of the morpholine mono-addition prodv The copolyuct ofmethylene-bis-acrylamide. mer thus obtained exhibited the samedye-recap} tive properties characteristic of the copolymers of thepresent invention.

Example 7.Formation of the cycloheazylaminef mono-addition product ofmethyZe-ne-bis-acrylamidc The procedure set forth in Example 1 is fol--lowed except that, as the reaction mixture, there is employed a solutionof 15.4 parts of methylenebis-acrylamide in a mixture of 280 parts ofwater and 160 parts of acetone to which solution there was added asolution of 11.9 parts of cyclohexyl amine in 49 parts of a 50%acetone-water mixture. The product resulting from such reaction is amaterial which consists essentially of a compound corresponding to theformula Example 8 A copolymer containing approximately 95% by weight ofacrylonitrile and approximately 5% by Weight of the cyclohexylaminemono-addition product of methylene-bis-acrylamide is obtained byreacting one part of the product of Example 7 with 19 parts ofacrylonitrile in accordance with the process set forth in Example 2. Thecopolymer thus formed is characterized by its afiinity for acid dyes.

As has been stated hereinbefore, the copolymerization products of thepresent invention contain principally acrylonitrile. The amount, withrespect to the acrylonitrile, in which the amine mono-addition productsof the methylene-bisacrylamides should be utilized in preparing thecopolymers will depend upon the qualities desired in the finishedproduct. It has been found that an amount of the mono-addition productcorresponding to at least 1% by weight of the acrylonitrile should beused to provide copolymers: which are particularly receptive of aciddyesp The receptivity or afiinity of the copolymers of the presentinvention for such dyes appears to increase as the ratio of themono-addition products to acrylonitrile in the copolymers increases.However, for best results, it is not preferred to employ amounts of themono-addition product substantially in excess of by weight of theacrylonitrile since there is no particular advantags to be gained in theuse of such amounts of the mono-addition product, and due to the furtherfact that such amounts of the mono-addition product tend to change thecharacter of the copolymer obtained.

The copolymers of the present invention may be cast into strong,flexible, self-supporting films or may be spun into fibers which may bemolecularly oriented as by cold drawing to provide fibers of hightensile strength, The solvents ordinarily employed in dry cleaningoperations have no appreciable effect upon either the copolymersthemselves or upon the color imparted to these 6 materials when they aredyed in accordance with the methods hereinbefore set forth. Therefore,fibers prepared from the copolymers of the present invention are ofobvious utility in the manufacture of wearing apparel, and haveparticular utility as a partial replacement for W001.

While the above products and processes of preparingthe same constitutepreferred embodiments of the present invention, changes may be madetherein without departing fromthe scope of the invention as defined inthe appended claims.

What is claimed is:

1. As a new product, a copolymerization product of from to 99% by weightof acrylonitrile with from 10% to 1% by weight of a compound of thegeneral formula HOR where R is a member of the group consisting ofhydrogen and methyl, and where Y is the residue of a compound selectedfrom the group consisting of aliphatic amines, alicyclic amines, andheterocyclic amines, the said amines having at least one hydrogenattached to the amino nitrogen atom, the point of attachment of the saidresidue being at the amino nitrogen thereof.

2. As a new product, a copolymerization product of from 90% to 99% byweight of acrylonitrile with from 10% to 1% by weight of a compound ofthe formula 3. As a new product, a copolymerization product of from 90%to 99% by weight of acrylonitrile with from 10% to 1% by weight of acompound of the formula 4. As a new product, a copolymerization productof from 90% to 99% by weight of acrylonitrile with from 10% to 1% byweight of a compound of the formula 5. As a new product, acopolymeri'zation product of from 90% to 99% by weight of acrylonitrilewith from 10% to 1% by weight of a compound of the formula ERNST ZERNER.MARK W. POLLOCK.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,478,378 Dickey Aug. 9, 19492,576,501 Dalton Nov. 27, 1951

1. AS A NEW PRODUCT, A COPOLYMERIZATION PRODUCT OF FROM 90% TO 99% BYWEIGHT OF A ACRYLONITRILE WITH FROM 10% TO 1% BY WEIGHT OF A COMPOUND OFTHE GENERAL FORMULA